U.S. patent number 9,522,855 [Application Number 14/361,552] was granted by the patent office on 2016-12-20 for process for producing low molecular weight ethylene- and alpha-olefin-based materials.
This patent grant is currently assigned to DOW GLOBAL TECHNOLOGIES LLC. The grantee listed for this patent is DOW GLOBAL TECHNOLOGIES LLC. Invention is credited to Jerzy Klosin, Pulikkottil J. Thomas.
United States Patent |
9,522,855 |
Klosin , et al. |
December 20, 2016 |
Process for producing low molecular weight ethylene- and
alpha-olefin-based materials
Abstract
The present invention generally relates to a process that
prepares polyethylenes, poly-.alpha.-olefins or
poly(co-ethylene-.alpha.-olefin) having backbone weight average
molecular weights less than 2500 daltons. The process uses a
metal-ligand complex as a precatalyst and can be carried out at
temperatures ranging from 30.degree. C. to 300.degree. C. The
relatively low molecular weight of the products enables improved
viscosity control for a wide variety of applications.
Inventors: |
Klosin; Jerzy (Midland, MI),
Thomas; Pulikkottil J. (Midland, MI) |
Applicant: |
Name |
City |
State |
Country |
Type |
DOW GLOBAL TECHNOLOGIES LLC |
Midland |
MI |
US |
|
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Assignee: |
DOW GLOBAL TECHNOLOGIES LLC
(Midland, MI)
|
Family
ID: |
47295214 |
Appl.
No.: |
14/361,552 |
Filed: |
November 28, 2012 |
PCT
Filed: |
November 28, 2012 |
PCT No.: |
PCT/US2012/066698 |
371(c)(1),(2),(4) Date: |
May 29, 2014 |
PCT
Pub. No.: |
WO2013/101375 |
PCT
Pub. Date: |
July 04, 2013 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20140357918 A1 |
Dec 4, 2014 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61581465 |
Dec 29, 2011 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F
10/00 (20130101); C07C 2/32 (20130101); C08F
10/00 (20130101); C08F 4/64186 (20130101); C08F
10/00 (20130101); C08F 4/64189 (20130101); C08F
10/00 (20130101); C08F 4/64193 (20130101); C08F
10/00 (20130101); C08F 4/64196 (20130101); C07C
2531/22 (20130101) |
Current International
Class: |
C08F
4/06 (20060101); C08F 10/00 (20060101); C07C
2/32 (20060101); C07C 2/26 (20060101); C08F
210/00 (20060101); C08F 4/18 (20060101) |
Field of
Search: |
;585/511
;526/107,100,348 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2005/108406 |
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Nov 2005 |
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WO |
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2007136497 |
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Nov 2007 |
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WO |
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WO 2007/136495 |
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Nov 2007 |
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WO |
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2011/146044 |
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Nov 2011 |
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WO |
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2013/101375 |
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Jul 2013 |
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WO |
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Other References
PCT/US2012/066698, International Search Report, mailed Feb. 5,
2013. cited by applicant .
PCT/US2012/066698, International Preliminary Report on
Patentability, mailed Jul. 20, 2014. cited by applicant.
|
Primary Examiner: Cheung; William
Attorney, Agent or Firm: Husch Blackwell LLP
Parent Case Text
This application is a U.S. National Stage Application under 35
U.S.C. .sctn.371 of International Application No. PCT/US2012/066698
filed on Nov. 28, 2012, which claims priority from the U.S.
Provisional Patent Application No. 61/581,465, on Dec. 29, 2011,
entitled "Process For Producing Low Molecular Weight Ethylene- and
Alpha-Olefin-Based Materials," the teachings of which are
incorporated by reference herein as if reproduced in full herein
below.
Claims
What is claimed is:
1. A process for preparing a low molecular weight ethylene-based
material comprising a step of contacting together (1) a monomer
selected from (a) ethylene; (b) a non-ethylene .alpha.-olefin; or
(c) a combination thereof; and (2) a catalytic amount of a
catalyst; wherein the catalyst comprises a mixture or reaction
product of ingredients (2a) and (2b) that is prepared before the
contacting step, wherein ingredient (2a) is at least one
metal-ligand complex, and wherein ingredient (2b) is at least one
activating co-catalyst; the metal-ligand complex of ingredient (2a)
being at least one metal-ligand complex of formula (I):
##STR00014## wherein M is titanium, zirconium, or hafnium, each
independently being in a formal oxidation state of +2, +3, or +4; n
is an integer from 0 to 3, wherein when n is 0, X is absent; each X
independently is a monodentate ligand that is neutral, monoanionic,
or dianionic, or two X are taken together to form a bidentate
ligand that is neutral, monoanionic, or dianionic; X and n are
chosen in such a way that the metal-ligand complex of formula (I)
is, overall, neutral; each Z independently is O, S,
N(C.sub.1-C.sub.40)hydrocarbyl, or P(C.sub.1-C.sub.40)hydrocarbyl;
L is (C.sub.1-C.sub.40)hydrocarbylene or
(C.sub.1-C.sub.40)heterohydrocarbylene, wherein the
(C.sub.1-C.sub.40)hydrocarbylene has a portion that comprises a
2-carbon atom linker backbone linking the Z atoms in formula (I)
and the (C.sub.1-C.sub.40)heterohydrocarbylene has a portion that
comprises a 2-atom atom linker backbone linking the Z atoms in
formula (I), wherein each atom of the 2-atom linker of the
(C.sub.1-C.sub.40)heterohydrocarbylene independently is a carbon
atom or a heteroatom, wherein each heteroatom independently is O,
S, S(O), S(O).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2,
P(R.sup.P), or N(R.sup.N), wherein independently each R.sup.C is
unsubstituted (C.sub.1-C.sub.18)hydrocarbyl or the two R.sup.C are
taken together to form a (C.sub.2-C.sub.19)alkylene, each R.sup.P
is unsubstituted (C.sub.1-C.sub.18)hydrocarbyl; and each R.sup.N is
unsubstituted (C.sub.1-C.sub.18)hydrocarbyl, a hydrogen atom or
absent; at least one of R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b
independently is a (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2,
OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, CN,
CF.sub.3, F.sub.3CO, halogen atom; and each of the others of
R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b independently is a
hydrogen, (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2,
OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or
halogen atom; each of R.sup.3a, R.sup.4a, R.sup.3b, R.sup.4b,
R.sup.6c, R.sup.7c, R.sup.8c, R.sup.6d, R.sup.7d, and R.sup.8d
independently is a hydrogen atom; (C.sub.1-C.sub.40)hydrocarbyl;
(C.sub.1-C.sub.40)heterohydrocarbyl; Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, P(R.sup.P).sub.2, N(R.sup.N).sub.2, OR.sup.C,
SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O)--,
R.sup.CS(O).sub.2--, (R.sup.C).sub.2C.dbd.N--, R.sup.CC(O)O--,
R.sup.COC(O)--, R.sup.CC(O)N(R)--, (R.sup.C).sub.2NC(O)-- or
halogen atom; each of R.sup.5c and R.sup.5d independently is a
(C.sub.6-C.sub.40)aryl or (C.sub.1-C.sub.40)heteroaryl; each of the
aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl,
hydrocarbylene, and heterohydrocarbylene groups independently is
unsubstituted or substituted with one or more substituents R.sup.S;
and each R.sup.S independently is a halogen atom, polyfluoro
substitution, perfluoro substitution, unsubstituted
(C.sub.1-C.sub.18)alkyl, F.sub.3C--, FCH.sub.2O--, F.sub.2HCO--,
F.sub.3CO--, R.sub.3Si--, R.sub.3Ge--, RO--, RS--, RS(O)--,
RS(O).sub.2--, R.sub.2P--, R.sub.2N--, R.sub.2C.dbd.N--, NC--,
RC(O)O--, ROC(O)--, RC(O)N(R)--, or R.sub.2NC(O)--, or two of the
R.sup.S are taken together to form an unsubstituted
(C.sub.1-C.sub.18)alkylene, wherein each R independently is an
unsubstituted (C.sub.1-C.sub.18)alkyl; such that the ratio of total
number of moles of the at least one metal-ligand complex (2a) to
total number of moles of the at least one activating co-catalyst
(2b) is from 1:10,000 to 100:1; under conditions such that a
polyethylene, poly-.alpha.-olefin, or
poly(co-ethylene-.alpha.-olefin), having a backbone weight average
molecular weight (Mw) that is less than 1500 daltons (Da), is
formed.
2. The process of claim 1 wherein M is zirconium or hafnium.
3. The process of claim 1 wherein each Z is O.
4. The process of claim 1 wherein R.sup.1a and R.sup.1b are methyl,
ethyl or isopropyl.
5. The process of claim 1 wherein R.sup.1a and R.sup.1b are
fluorine atoms, chlorine atoms, bromine atoms or iodine atoms.
6. The process of claim 1 wherein L is --CH.sub.2CH.sub.2--,
--CH(CH.sub.3)CH(CH.sub.3)--, 1,2-cyclopentanediyl or
1,2-cyclohexane-diyl.
7. The process of claim 1 wherein R.sup.5d independently is a
2,7-disubstituted 9H-carbazol-9-yl or a 3,6-disubstituted
9H-carbazol-9-yl, 9H-carbazol-9-yl, wherein each substituent is
R.sup.S.
8. The process of claim 1 wherein R.sup.5d independently is a
(C.sub.6-C.sub.40)aryl that is a 2,4-disubstituted phenyl, wherein
each substituent is R.sup.S; 2,5-disubstituted phenyl wherein each
substituent is R.sup.S; 2,6-disubstituted phenyl wherein each
substituent is R.sup.S; 3,5-disubstituted phenyl wherein each
substituent is R.sup.S; 2,4,6-trisubstituted phenyl wherein each
substituent is R.sup.S; naphthyl or substituted naphthyl wherein
each substituent is R.sup.S; 1,2,3,4-tetrahydronaphthyl;
anthracenyl; 1,2,3,4-tetrahydroanthracenyl;
1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrenyl; or
1,2,3,4,5,6,7,8-octahydrophenanthrenyl.
9. The process of claim 1 wherein the conditions include a
temperature from 30.degree. C. to 300.degree. C.
Description
The present invention relates to a process for preparing low
molecular weight polyethylene, poly-.alpha.-olefins and
poly(co-ethylene-.alpha.-olefins) at a wide range of reactor
temperatures.
Low molecular weight ethylene-based polymers are highly desirable
due to their potential use in many applications such as, for
example, synthetic oils in automotive applications, transformer
fluids in electrical applications, lubricants, adhesives and high
temperature fluids. Most processes that produce such a low
molecular ethylene-based materials are produced at temperatures
below 100.degree. C. From the process prospective, it might be
desirable to produce such ethylene-based materials at higher
reactor temperature. Such temperatures are defined as above about
100 degrees Celsius (.degree. C.), and generally up to about
250.degree. C.
In view of this, researchers have sought ways to produce low
molecular weight ethylene-based products while still enjoying the
benefits of high temperature processing, such as rapid
polymerization. Various forays into the catalyst art have, in
general, resulted in products of various molecular weights, but
none has to date resulted in high temperature application to
produce very low molecular weight polymers.
In view of this, researchers have sought ways to produce low
molecular weight ethylene-based products while still enjoying the
benefits of high temperature processing, such as rapid
polymerization. Various forays into the catalyst art have, in
general, resulted in products of various molecular weights, but
none has to date resulted in high temperature application to
produce very low molecular weight polymers. Among these forays are,
for example, U.S. Pat. Nos. 6,869,904 and 7,060,848. These patents
disclose ligands, and metal-ligand complexes with substituted
bridged bis-aromatic or bridged bis-bi-aromatic ligands. As
catalysts, these complexes offer high comonomer incorporation into
ethylene/.alpha.-olefin copolymers, where such olefins are, for
example, 1-octene, propylene or styrene.
In one aspect, the present invention is a process for preparing a
low molecular weight ethylene-based material comprising a step of
contacting together (1) a monomer selected from (a) ethylene; (b) a
non-ethylene .alpha.-olefin; or (c) a combination thereof; and (2)
a catalytic amount of a catalyst; wherein the catalyst comprises a
mixture or reaction product of ingredients (2a) and (2b) that is
prepared before the contacting step, wherein ingredient (2a) is at
least one metal-ligand complex, and wherein ingredient (2b) is at
least one activating co-catalyst; the metal-ligand complex of
ingredient (2a) being at least one metal-ligand complex of formula
(I):
##STR00001## wherein M is titanium, zirconium, or hafnium, each
independently being in a formal oxidation state of +2, +3, or +4; n
is an integer from 0 to 3, wherein when n is 0, X is absent; each X
independently is a monodentate ligand that is neutral, monoanionic,
or dianionic, or two X are taken together to form a bidentate
ligand that is neutral, monoanionic, or dianionic; X and n are
chosen in such a way that the metal-ligand complex of formula (I)
is, overall, neutral; each Z independently is O, S,
N(C.sub.1-C.sub.40)hydrocarbyl, or P(C.sub.1-C.sub.40)hydrocarbyl;
L is (C.sub.1-C.sub.40)hydrocarbylene or
(C.sub.1-C.sub.40)heterohydrocarbylene, wherein the
(C.sub.1-C.sub.40)hydrocarbylene has a portion that comprises a
2-carbon atom linker backbone linking the Z atoms in formula (I)
and the (C.sub.1-C.sub.40)heterohydrocarbylene has a portion that
comprises a 2-atom atom linker backbone linking the Z atoms in
formula (I), wherein each atom of the 2-atom linker of the
(C.sub.1-C.sub.40)heterohydrocarbylene independently is a carbon
atom or a heteroatom, wherein each heteroatom independently is O,
S, S(O), S(O).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2,
P(R.sup.P), or N(R.sup.N), wherein independently each R.sup.C is
unsubstituted (C.sub.1-C.sub.18)hydrocarbyl or the two R.sup.C are
taken together to form a (C.sub.2-C.sub.19)alkylene, each R.sup.P
is unsubstituted (C.sub.1-C.sub.18)hydrocarbyl; and each R.sup.N is
unsubstituted (C.sub.1-C.sub.18)hydrocarbyl, a hydrogen atom or
absent; at least one of R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b
independently is a (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2,
OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, CN,
CF.sub.3, F.sub.3CO, halogen atom, and each of the others of
R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b independently is a
hydrogen, (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2,
OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or
halogen atom; each of R.sup.3a, R.sup.4a, R.sup.3b, R.sup.4b,
R.sup.6c, R.sup.7c, R.sup.8c, R.sup.6d, R.sup.7d, and R.sup.8d
independently is a hydrogen atom; (C.sub.1-C.sub.40)hydrocarbyl;
(C.sub.1-C.sub.40)heterohydrocarbyl; Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, P(R.sup.P).sub.2, N(R.sup.N).sub.2, OR.sup.C,
SR.sup.C, NO.sub.2, CN, CF.sub.3, R.sup.CS(O)--,
R.sup.CS(O).sub.2--, (R.sup.C).sub.2C.dbd.N--, R.sup.CC(O)O--,
R.sup.COC(O)--, R.sup.CC(O)N(R)--, (R.sup.C).sub.2NC(O)-- or
halogen atom; each of R.sup.5c and R.sup.5d independently is a
(C.sub.6-C.sub.40)aryl or (C.sub.1-C.sub.40)heteroaryl; each of the
aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl,
hydrocarbylene, and heterohydrocarbylene groups independently is
unsubstituted or substituted with one or more substituents R.sup.S;
and each R.sup.S independently is a halogen atom, polyfluoro
substitution, perfluoro substitution, unsubstituted
(C.sub.1-C.sub.18)alkyl, F.sub.3C--, FCH.sub.2O--, F.sub.2HCO--,
F.sub.3CO--, R.sub.3Si--, R.sub.3Ge--, RO--, RS--, RS(O)--,
RS(O).sub.2--, R.sub.2P--, R.sub.2N--, R.sub.2C.dbd.N--, NC--,
RC(O)O--, ROC(O)--, RC(O)N(R)--, or R.sub.2NC(O)--, or two of the
R.sup.S are taken together to form an unsubstituted
(C.sub.1-C.sub.18)alkylene, wherein each R independently is an
unsubstituted (C.sub.1-C.sub.18)alkyl; such that the ratio of total
number of moles of the at least one metal-ligand complex of (2a) to
total number of moles of the at least one activating co-catalyst of
(2b) is from 1:10,000 to 100:1; under conditions such that a
polyethylene, poly-.alpha.-olefin, or,
poly(co-ethylene-.alpha.-olefin), having a backbone weight average
molecular weight (Mw) that is less than 2500 daltons (Da), is
formed.
The invention offers a process to prepare low molecular weight
polymers based on ethylene, an .alpha.-olefin, or both, using as a
catalyst one or more of a group of compounds having in common (1) a
two-atom bridge between bis-ether oxygen atoms, and (2) a
substituent group positioned ortho and/or meta to the di-ether
bridge. These two features, in particular, have been found to
afford these catalysts with a unique capability to produce
surprisingly low molecular weight polyethylene,
poly(co-ethylene-.alpha.-olefins) and poly-.alpha.-olefins,
generally having backbone weight average molecular weights less
than 2500 Da, preferably less than 1500 Da, even when processing is
accomplished over a wide range of temperatures ranging from
30.degree. C. to 300.degree. C. Because of their surprisingly low
molecular weights, these products exhibit controlled viscosity and
are generally liquids, increasing the number of potential
applications for them. The term "low molecular weights" refers to
materials which may include dimers, trimers, tetramers, etc., up to
backbone weight average molecular weights of less than 2500 Da.
Preparation of the low molecular weight polyethylene,
poly(.alpha.-olefin) or poly(co-ethylene-.alpha.-olefin) herein is
generally by contact between the selected catalyst or catalysts and
the other starting ingredients, with a first step comprising
contacting the metal-ligand complex with a suitable activating
co-catalyst to form a catalyst, followed by contact between the
catalyst, or catalysts, and either the ethylene or the selected
combination of ethylene and at least one .alpha.-olefin, under
suitable reaction conditions to form the final desired product.
In general the catalysts useful in the present invention fall
within the group defined by co-pending U.S. Patent Publication No.
2011/0282018, filed May 11, 2011. However, the catalysts used
herein form a subset thereof that exhibits surprising capabilities
not shared by other members of that group, notably to make a
polyethylene, a poly(.alpha.-olefin) or a
poly(co-ethylene-.alpha.-olefin) that has a surprisingly low
molecular weight.
In some embodiments, each of the chemical groups (e.g., X, L,
R.sup.1a, etc.) of the metal-ligand complex of formula (I) is
unsubstituted, that is, can be defined without use of a substituent
R.sup.S. In other embodiments, at least one of the chemical groups
of the metal-ligand complex independently contains one or more of
the substituents R.sup.S. Preferably, there are not more than a
total of 20 R.sup.S, more preferably not more than 10 R.sup.S, and
still more preferably not more than 5 R.sup.S. Where the invention
compound contains two or more substituents R.sup.S, each R.sup.S
independently is bonded to a same or different substituted chemical
group. When two or more R.sup.S are bonded to a same chemical
group, they independently are bonded to a same or different carbon
atom or heteroatom in the same chemical group, up to and including
persubstitution of the chemical group.
The terms "persubstitution" means each hydrogen atom (H) bonded to
a carbon atom or heteroatom of a corresponding unsubstituted
compound or functional group is replaced by a substituent (e.g.,
R.sup.S). The term, "polysubstitution" means at least two, but not
all, hydrogen atoms (H) bonded to carbon atoms or heteroatoms of a
corresponding unsubstituted compound or functional group are
replaced by substituents (e.g., R.sup.S). In some embodiments, at
least one R.sup.S is polyfluoro substitution or perfluoro
substitution.
As used herein, "polyfluoro substitution" and "perfluoro
substitution" each count as one R.sup.S substituent. In some
embodiments each R.sup.S independently is selected from a group
consisting of a halogen atom and any one of polyfluoro
substitution, unsubstituted (C.sub.1-C.sub.18)alkyl, F.sub.3C--,
FCH.sub.2O--, F.sub.2HCO--, F.sub.3CO--, R.sub.3Si--, R.sub.3Ge--,
RO--, RS--, RS(O)--, RS(O).sub.2--, R.sub.2P--, R.sub.2N--,
R.sub.2C.dbd.N--, NC--, RC(O)O--, ROC(O)--, RC(O)N(R)--, and
R.sub.2NC(O)--, wherein each R independently is an unsubstituted
(C.sub.1-C.sub.18)alkyl. In some embodiments each R.sup.S
independently is selected from a group consisting of a halogen
atom, unsubstituted (C.sub.1-C.sub.18)alkyl, and any one of
polyfluoro substitution, F.sub.3C--, FCH.sub.2O--, F.sub.2HCO--,
F.sub.3CO--, R.sub.3Si--, R.sub.3Ge--, RO--, RS--, RS(O)--,
RS(O).sub.2--, R.sub.2P--, R.sub.2N--, R.sub.2C.dbd.N--, NC--,
RC(O)O--, ROC(O)--, RC(O)N(R)--, and R.sub.2NC(O)--. In some
embodiments each R.sup.S independently is selected from a group
consisting of an unsubstituted (C.sub.1-C.sub.18)alkyl and any one
of F.sub.3C--, FCH.sub.2O--, F.sub.2HCO--, F.sub.3CO--,
R.sub.3Si--, R.sub.3Ge--, RO--, RS--, RS(O)--, RS(O).sub.2--,
R.sub.2P--, R.sub.2N--, R.sub.2C.dbd.N--, NC--, RC(O)O--, ROC(O)--,
RC(O)N(R)--, and R.sub.2NC(O)--. In some embodiments two R.sup.S
are taken together to form an unsubstituted
(C.sub.1-C.sub.18)alkylene. Still more preferably substitutents
R.sup.S independently are unsubstituted (C.sub.1-C.sub.18)alkyl, F,
unsubstituted (C.sub.1-C.sub.18)alkylene, or a combination thereof;
and even more preferably unsubstituted (C.sub.1-C.sub.8)alkyl or
unsubstituted (C.sub.1-C.sub.8)alkylene. The
(C.sub.1-C.sub.18)alkylene and (C.sub.1-C.sub.8)alkylene
substituents are especially useful for forming substituted chemical
groups that are bicyclic or tricyclic analogs of corresponding
monocyclic or bicyclic unsubstituted chemical groups.
The term "hydrocarbylene" means a hydrocarbon diradical having at
least one carbon atom, such that each hydrocarbon diradical
independently is aromatic or non-aromatic; saturated or
unsaturated; straight chain or branched chain; cyclic or acyclic;
unsubstituted or substituted; or a combination of at least two
thereof. The radicals of the hydrocarbon diradical can be on a
single carbon atom or, preferably, different carbon atoms. The term
"alkylene" is a hydrocarbylene wherein the hydrocarbon diradical is
non-aromatic, saturated, straight chain or branched, acyclic, and
unsubstituted or substituted. The term "hydrocarbyl" is as defined
previously for hydrocarbylene, except where hydrocarbylene is the
diradical, the hydrocarbyl is a monoradical and thus has a hydrogen
atom in place of the second radical of the diradical. The term
"alkyl" is a hydrocarbyl wherein the hydrocarbon radical is
non-aromatic, saturated, straight chain or branched, acyclic, and
unsubstituted or substituted. Preferably, the substituent of the
substituted alkyl is aryl. The term "heterohydrocarbylene" means a
heterohydrocarbon diradical having at least one carbon atom and
from 1 to 6 heteroatoms, wherein each heterohydrocarbon diradical
independently is aromatic or non-aromatic; saturated or
unsaturated; straight chain or branched chain; cyclic or acyclic;
unsubstituted or substituted; or a combination of at least two
thereof. The radicals of the heterohydrocarbon diradical can be on
a single atom or, preferably, different atoms, each radical-bearing
atom independently being carbon or heteroatom. The term
"heterohydrocarbyl" is as defined previously for
heterohydrocarbylene, except where heterohydrocarbylene is the
diradical, the heterohydrocarbyl is a monoradical.
In some embodiments the present invention contemplates such
unsubstituted chemical groups or molecules having a lower limit of
at least 1 carbon atom. However, the invention includes embodiments
having higher lower limits (e.g., at least any one of 2, 3, 4, 5,
6, 7, and 8 carbons). In particular, embodiments including higher
lower limits as would be well known for a smallest aspect of the
chemical group or molecule (e.g., at least 3 carbons for a
cycloalkyl or .alpha.-olefin) may be particularly preferred.
Preferably, each hydrocarbyl independently is an unsubstituted or
substituted alkyl, cycloalkyl (having at least 3 carbon atoms),
(C.sub.3-C.sub.20)cycloalkyl-(C.sub.1-C.sub.20)alkylene, aryl
(having at least 6 carbon atoms), or
(C.sub.6-C.sub.20)aryl-(C.sub.1-C.sub.20)alkylene. Preferably, each
of the aforementioned hydrocarbyl groups independently has a
maximum of 40, more preferably 20, and still more preferably 12
carbon atoms.
Preferably, each alkyl independently has a maximum of 40, more
preferably 20, sill more preferably 12, and still more preferably 8
carbon atoms. A few non-limiting examples of unsubstituted
(C.sub.1-C.sub.40)alkyl include unsubstituted
(C.sub.1-C.sub.20)alkyl; unsubstituted (C.sub.1-C.sub.10)alkyl;
unsubstituted (C.sub.1-C.sub.5)alkyl; methyl; ethyl; 1-propyl;
2-methylpropyl; 1,1-dimethylethyl; and 1-heptyl. Non-limiting
examples of substituted (C.sub.1-C.sub.40)alkyl include substituted
(C.sub.1-C.sub.20)alkyl, substituted (C.sub.1-C.sub.10)alkyl,
trifluoromethyl, and (C.sub.45)alkyl. The (C.sub.45)alkyl may be,
for example, a (C.sub.27-C.sub.40)alkyl substituted by one R.sup.S,
which is a (C.sub.18-C.sub.5)alkyl, respectively. Preferably, each
(C.sub.1-C.sub.5)alkyl independently is methyl, trifluoromethyl,
ethyl, 1-propyl, 2-methylethyl, or 1,1-dimethylethyl.
Preferably, each aryl independently has from 6 to 40 carbon atoms.
The term "(C.sub.6-C.sub.40)aryl" means an unsubstituted or
substituted (by at least one R.sup.S) mono-, bi- or tricyclic
aromatic hydrocarbon radical of from 6 to 40, preferably from 6 to
14, ring carbon atoms, and the mono-, bi- or tricyclic radical
comprises 1, 2 or 3 rings, respectively, wherein the 1 ring is
aromatic; at least one of the 2 or 3 rings is aromatic; and the 2
or 3 rings independently are fused or non-fused. Other aryl groups
(e.g., (C.sub.6-C.sub.10)aryl)) are defined in an analogous manner.
Preferably, (C.sub.6-C.sub.40)aryl has a maximum of 20 carbon atoms
(i.e., (C.sub.6-C.sub.20)aryl), more preferably 10 carbon atoms,
and still more preferably 6 carbon atoms. Non-limiting examples of
unsubstituted (C.sub.6-C.sub.40)aryl include unsubstituted
(C.sub.6-C.sub.20)aryl; unsubstituted (C.sub.6-C.sub.18)aryl;
phenyl; (C.sub.3-C.sub.6)cycloalkyl-phenyl; fluorenyl;
tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl;
dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene.
Examples of substituted (C.sub.6-C.sub.40)aryl are substituted
(C.sub.6-C.sub.20)aryl; substituted (C.sub.6-C.sub.18)aryl;
2-(C.sub.1-C.sub.5)alkyl-phenyl;
2,4-bis(C.sub.1-C.sub.5)alkyl-phenyl;
2,4-bis[(C.sub.20)alkyl]-phenyl; polyfluorophenyl;
pentafluorophenyl; and fluoren-9-one-1-yl.
Preferably, each cycloalkyl independently has from 3 to 40 carbon
atoms. The term "(C.sub.3-C.sub.40)cycloalkyl" means a saturated
cyclic hydrocarbon radical of from 3 to 40 carbon atoms that is
unsubstituted or substituted by at least one R.sup.S. Other
cycloalkyl groups (e.g., (C.sub.3-C.sub.12)alkyl)) are defined in
an analogous manner. Preferably, (C.sub.3-C.sub.40)cycloalkyl has a
maximum of 20 carbon atoms (i.e., (C.sub.3-C.sub.30)cycloalkyl),
and more preferably 6 carbon atoms. Non-limiting examples of
unsubstituted (C.sub.3-C.sub.40)cycloalkyl include unsubstituted
(C.sub.3-C.sub.20)cycloalkyl, unsubstituted
(C.sub.3-C.sub.10)cycloalkyl, cyclopropyl, and cyclodecyl. Examples
of substituted (C.sub.3-C.sub.40)cycloalkyl are substituted
(C.sub.3-C.sub.20)cycloalkyl, substituted
(C.sub.3-C.sub.10)cycloalkyl, cyclopentanon-2-yl, and
1-fluorocyclohexyl.
Preferably, each hydrocarbylene independently has from 1 to 40
carbon atoms. Examples of (C.sub.1-C.sub.40)hydrocarbylene are
unsubstituted or substituted (C.sub.6-C.sub.40)arylene,
(C.sub.3-C.sub.40)cycloalkylene, and (C.sub.1-C.sub.40)alkylene
(e.g., (C.sub.1-C.sub.20)alkylene). In some embodiments, the
diradicals are on a same carbon atom (e.g., --CH.sub.2--) or on
adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart
by one, two, etc., intervening carbon atoms (e.g., respective
1,3-diradicals, 1,4-diradicals, etc.). Preferred is a 1,2-, 1,3-,
1,4-, or an .alpha.-, .omega.-diradical, and more preferably a
1,2-diradical. The .alpha.-, .omega.-omega-diradical is a diradical
that has a maximum carbon backbone spacing between the radical
carbons. More preferred is a 1,2-diradical version of
(C.sub.6-C.sub.18)arylene, (C.sub.3-C.sub.20)cycloalkylene, or
(C.sub.2-C.sub.20)alkylene; a 1,3-diradical version of
(C.sub.6-C.sub.18)arylene, (C.sub.4-C.sub.20)cycloalkylene, or
(C.sub.3-C.sub.20)alkylene; or a 1,4-diradical version of
(C.sub.6-C.sub.18)arylene, (C.sub.6-C.sub.20)cycloalkylene, or
(C.sub.4-C.sub.20)alkylene.
Preferably, each alkylene independently has from 1 to 40 carbon
atoms. The term "(C.sub.1-C.sub.40)alkylene" means a saturated
straight chain or branched chain diradical (i.e., the radicals are
not on ring atoms) of from 1 to 40 carbon atoms that is
unsubstituted or substituted by at least one R.sup.S. Other
alkylene groups (e.g., (C.sub.1-C.sub.12)alkylene)) are defined in
an analogous manner. Examples of unsubstituted
(C.sub.1-C.sub.40)alkylene are unsubstituted
(C.sub.1-C.sub.20)alkylene, including unsubstituted
1,2-(C.sub.2-C.sub.10)alkylene; 1,3-(C.sub.3-C.sub.10)alkylene;
1,4-(C.sub.4-C.sub.10)alkylene; --CH.sub.2--, --CH.sub.2CH.sub.2--,
--(CH.sub.2).sub.3, --CH.sub.2CHCH.sub.3, --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.5--, --(CH.sub.2).sub.6--, --(CH.sub.2).sub.7--,
--(CH.sub.2).sub.8--, and --(CH.sub.2).sub.4C(H)(CH.sub.3)--.
Examples of substituted (C.sub.1-C.sub.40)alkylene are substituted
(C.sub.1-C.sub.20)alkylene, --CF.sub.2--, --C(O)--, and
--(CH.sub.2).sub.14C(CH.sub.3).sub.2(CH.sub.2).sub.5-- (i.e., a
6,6-dimethyl substituted normal-1,20-eicosylene). Since as
mentioned previously two R.sup.S may be taken together to form a
(C.sub.1-C.sub.18)alkylene, examples of substituted
(C.sub.1-C.sub.40)alkylene also include
1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane,
2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and
2,3-bis(methylene)bicyclo[2.2.2]octane.
Preferably, each cycloalkylene independently has from 3 to 40
carbon atoms. The term "(C.sub.3-C.sub.40)cycloalkylene" means a
cyclic diradical (i.e., the radicals are on ring atoms) that is
unsubstituted or substituted by at least one R.sup.S. Examples of
unsubstituted (C.sub.3-C.sub.40)cycloalkylene are
1,3-cyclopropylene, 1,1-cyclopropylene, and 1,2-cyclohexylene.
Examples of substituted (C.sub.3-C.sub.40)cycloalkylene are
2-oxo-1,3-cyclopropylene and 1,2-dimethyl-1,2-cyclohexylene.
Preferably, each heterohydrocarbyl independently has from 1 to 40
carbon atoms. The term "(C.sub.1-C.sub.40)heterohydrocarbyl" means
a heterohydrocarbon radical and the term
"(C.sub.1-C.sub.40)heterohydrocarbylene" means a heterohydrocarbon
diradical, and each heterohydrocarbon independently has at least
one heteroatom B(R.sup.C)O; S; S(O); S(O).sub.2; Si(R.sup.C).sub.2;
Ge(R.sup.C).sub.2; P(R.sup.P); and N(R.sup.N), wherein
independently each R.sup.C is unsubstituted
(C.sub.1-C.sub.18)hydrocarbyl, each R.sup.P is unsubstituted
(C.sub.1-C.sub.18)hydrocarbyl; and each R.sup.N is unsubstituted
(C.sub.1-C.sub.18)hydrocarbyl or absent (e.g., absent when N
comprises --N.dbd. or tri-carbon substituted N). The radicals of
the diradical can be on same or different type of atoms (e.g., both
on saturated acyclic atoms or one on an acyclic atom and one on
aromatic atom). Other heterohydrocarbyl (e.g., (C.sub.1-C.sub.12)
heterohydrocarbyl)) and heterohydrocarbylene groups are defined in
an analogous manner. Preferably, the heteroatom(s) is O; S; S(O);
S(O).sub.2; Si(R.sup.C).sub.2; P(R.sup.P); or N(R.sup.N). The
heterohydrocarbon radical and each of the heterohydrocarbon
diradicals independently is on a carbon atom or heteroatom thereof,
although preferably each is on a carbon atom when bonded to a
heteroatom in formula (I) or to a heteroatom of another
heterohydrocarbyl or heterohydrocarbylene. Each
(C.sub.1-C.sub.40)heterohydrocarbyl and
(C.sub.1-C.sub.40)heterohydrocarbylene independently is
unsubstituted or substituted (by at least one R.sup.S), aromatic or
non-aromatic, saturated or unsaturated, straight chain or branched
chain, cyclic (including mono- and poly-cyclic, fused and non-fused
polycyclic) or acyclic, or a combination of two or more thereof;
and each is respectively the same as or different from another.
Preferably, each heteroaryl independently has from 1 to 40 carbon
atoms. The term "(C.sub.1-C.sub.40)heteroaryl" means an
unsubstituted or substituted (by at least one R.sup.S) mono-, bi-
or tricyclic heteroaromatic hydrocarbon radical of from 1 to 40
total carbon atoms and from 1 to 4 heteroatoms; from 1 to 44 total
ring atoms, preferably from 5 to 10 total ring atoms, and the
mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings,
respectively, wherein the 1-ring is heteroaromatic; at least one of
the 2 or 3 rings is heteroaromatic; and the 2 or 3 rings
independently are fused or non-fused. Other heteroaryl groups
(e.g., (C.sub.1-C.sub.12)heteroaryl)) are defined in an analogous
manner. The monocyclic heteroaromatic hydrocarbon radical is a
5-membered or 6-membered ring. The 5-membered ring has from 1 to 4
carbon atoms and from 4 to 1 heteroatoms, respectively, each
heteroatom being O, S, N, or P, and preferably O, S, or N. Examples
of 5-membered ring heteroaromatic hydrocarbon radical are
pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl;
isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl;
thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl;
1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and
tetrazol-5-yl. The 6-membered ring has 4 or 5 carbon atoms and 2 or
1 heteroatoms, the heteroatoms being N or P, and preferably N.
Examples of 6-membered ring heteroaromatic hydrocarbon radical are
pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic
heteroaromatic hydrocarbon radical preferably is a fused 5,6- or
6,6-ring system. Examples of the fused 5,6-ring system bicyclic
heteroaromatic hydrocarbon radical are indol-1-yl; and
benzimidazole-1-yl. Examples of the fused 6,6-ring system bicyclic
heteroaromatic hydrocarbon radical are quinolin-2-yl; and
isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical
preferably is a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system.
An example of the fused 5,6,5-ring system is
1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of the fused
5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of the fused
6,5,6-ring system is 9H-carbazol-9-yl, which may also be named as a
dibenzo-1H-pyrrole-1-yl. An example of the fused 6,5,6-ring system
is 9H-carbazol-9-yl. An example of the fused 6,6,6-ring system is
acrydin-9-yl. The 5-membered rings and 6-membered rings of the
fused 5,6-; 6,6-; 5,6,5-; 5,6,6-; 6,5,6-; and 6,6,6-ring systems
independently can be as described above for 5-membered and
6-membered rings, respectively, except where the ring fusions
occur.
The aforementioned heteroalkyl and heteroalkylene groups are
saturated straight or branched chain radicals or diradicals,
respectively, containing at least one carbon atom and at least one
heteroatom (up to 4 heteroatoms) Si(R.sup.C).sub.2,
Ge(R.sup.C).sub.2, P(R.sup.P), N(R.sup.N), N, O, S, S(O), and
S(O).sub.2 as defined above, wherein each of the heteroalkyl and
heteroalkylene groups independently are unsubstituted or
substituted by at least one R.sup.S.
Unless otherwise indicated herein the term "heteroatom" means O, S,
S(O), S(O).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2, P(R.sup.P),
or N(R.sup.N), wherein independently each R.sup.C is unsubstituted
(C.sub.1-C.sub.18)hydrocarbyl or the two R.sup.C are taken together
to form a (C.sub.2-C.sub.19)alkylene (e.g., the two R.sup.C
together with the silicon atom to which they are both bonded form a
3-membered to 20-membered silacycloalkyl), each R.sup.P is
unsubstituted (C.sub.1-C.sub.18)hydrocarbyl; and each R.sup.N is
unsubstituted (C.sub.1-C.sub.18)hydrocarbyl, a hydrogen atom, or
absent (absent when N comprises --N.dbd. as in a N-containing
heteroaryl).
Preferably, there are no O--O, S--S, or O--S bonds, other than O--S
bonds in an S(O) or S(O).sub.2 diradical functional group, in the
metal-ligand complex of formula I. More preferably, there are no
O--O, N--N, P--P, N--P, S--S, or O--S bonds, other than O--S bonds
in an S(O) or S(O).sub.2 diradical functional group, in the
metal-ligand complex of formula I.
The term "saturated" means lacking carbon-carbon double bonds,
carbon-carbon triple bonds, and (in heteroatom-containing groups)
carbon-nitrogen, carbon-phosphorus, and carbon-silicon double
bonds. Where a saturated chemical group is substituted by one or
more substituents R.sup.S, one or more double and/or triple bonds
optionally may or may not be present in substituents R.sup.S. The
term "unsaturated" means containing one or more carbon-carbon
double bonds, carbon-carbon triple bonds, and (in
heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus,
and carbon-silicon double bonds, not including any such double
bonds that may be present in substituents R.sup.S, if any, or in
(hetero)aromatic rings, if any.
In the metal-ligand complex of formula (I) certain variables and
chemical groups n, M, X, Z, L, R.sup.1a, R.sup.2a, R.sup.3a,
R.sup.4a, R.sup.1b, R.sup.2b, R.sup.3b, R.sup.4b, R.sup.5c,
R.sup.6c, R.sup.7c, R.sup.8c, R.sup.5d, R.sup.6d, R.sup.7d, and
R.sup.8d, as the formulas allow, are preferred. Examples of such
preferred groups follow.
Preferably M is zirconium or hafnium. The formal oxidation state of
M may vary as +2 or +4. Any combination of a preferred M and a
preferred formal oxidation state may be employed.
In various embodiments n may be 0, 1, 2, or 3.
Certain X groups are preferred. In some embodiments each X
independently is the monodentate ligand. Preferably when there are
two or more X monodentate ligands, each X is the same. In some
embodiments the monodentate ligand is the monoanionic ligand. The
monoanionic ligand has a net formal oxidation state of -1. Each
monoanionic ligand preferably independently is hydride, hydrocarbyl
carbanion, heterohydrocarbyl carbanion, halide, nitrate, carbonate,
phosphate, sulfate, HC(O)O.sup.-, hydrocarbylC(O)O.sup.-,
HC(O)N(H).sup.-, hydrocarbylC(O)N(H).sup.-,
hydrocarbylC(O)N-(C.sub.1-C.sub.20)hydrocarbyl).sup.-,
R.sup.KR.sup.LB.sup.-, R.sup.KR.sup.LN.sup.-, R.sup.KO.sup.-,
R.sup.KS.sup.-, R.sup.KR.sup.LP.sup.-, or
R.sup.MR.sup.KR.sup.LSi.sup.-, wherein each R.sup.K, R.sup.L, and
R.sup.M independently is hydrogen, hydrocarbyl, or
heterohydrocarbyl, or R.sup.K and R.sup.L are taken together to
form a (C.sub.2-C.sub.40)hydrocarbylene or heterohydrocarbylene and
R.sup.M is as defined above.
In some embodiments at least one monodentate ligand of X
independently is the neutral ligand. Preferably the neutral ligand
is a neutral Lewis base group that is R.sup.XNR.sup.KR.sup.L,
R.sup.KOR.sup.L, R.sup.KSR.sup.L, or R.sup.XPR.sup.KR.sup.L,
wherein each R.sup.X independently is hydrogen, hydrocarbyl,
[(C.sub.1-C.sub.10)hydrocarbyl].sub.3Si,
[(C.sub.1-C.sub.10)hydrocarbyl].sub.3Si(C.sub.1-C.sub.10)hydrocarbyl,
or heterohydrocarbyl and each R.sup.K and R.sup.L independently is
as defined above.
In some embodiments, each X is a monodentate ligand that
independently is a halogen atom, unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl, unsubstituted
(C.sub.1-C.sub.20)hydrocarbylC(O)O--, or R.sup.KR.sup.LN-- wherein
each of R.sup.K and R.sup.L independently is an unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. In some embodiments each monodentate
ligand X is a chlorine atom, (C.sub.1-C.sub.10)hydrocarbyl (e.g.,
(C.sub.1-C.sub.6)alkyl or benzyl), unsubstituted
(C.sub.1-C.sub.10)hydrocarbylC(O)O--, or R.sup.KR.sup.LN-- wherein
each of R.sup.K and R.sup.L independently is an unsubstituted
(C.sub.1-C.sub.10)hydrocarbyl.
In some embodiments there are at least two X and the two X are
taken together to form the bidentate ligand. In some embodiments
the bidentate ligand is a neutral bidentate ligand. Preferably the
neutral bidentate ligand is a diene of formula
(R.sup.D).sub.2C.dbd.C(R.sup.D)--C(R.sup.D).dbd.C(R.sup.D).sub.2,
wherein each R.sup.D independently is H, unsubstituted
(C.sub.1-C.sub.6)alkyl, phenyl, or naphthyl. In some embodiments
the bidentate ligand is a monoanionic-mono(Lewis base) ligand. The
monoanionic-mono(Lewis base) ligand preferably is a 1,3-dionate of
formula (D): R.sup.E--C(O.sup.-).dbd.CH--C(.dbd.O)--R.sup.E (D),
wherein each R.sup.D independently is H, unsubstituted
(C.sub.1-C.sub.6)alkyl, phenyl, or naphthyl. In some embodiments
the bidentate ligand is a dianionic ligand. The dianionic ligand
has a net formal oxidation state of -2. Preferably each dianionic
ligand independently is carbonate, oxalate (i.e.,
.sup.-O.sub.2CC(O)O.sup.--), (C.sub.2-C.sub.40)hydrocarbylene
dicarbanion, heterohydrocarbylene dicarbanion, phosphate, or
sulfate.
As previously mentioned, number and charge (neutral, monoanionic,
dianionic) of X are selected depending on the formal oxidation
state of M such that the metal-ligand complex of formula (I) is,
overall, neutral.
In some embodiments each X is the same, wherein each X is methyl;
ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl;
trimethylsilylmethyl; phenyl; benzyl; or chloro. In some
embodiments n is 2 and each X is the same.
In some embodiments at least two X are different. In some
embodiments n is 2 and each X is a different one of methyl; ethyl;
1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl;
trimethylsilylmethyl; phenyl; benzyl; and chloro.
The integer n indicates number of X. Preferably n is 2 or 3 and at
least two X independently are monoanionic monodentate ligands and a
third X, if present, is a neutral monodentate ligand. In some
embodiments n is 2 at two X are taken together to form a bidentate
ligand. In some embodiments the bidentate ligand is
2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.
In some embodiments L is two-carbon atom hydrocarbylene. In some
embodiments L comprises the 2-carbon atom linker backbone (e.g., L
is --CH.sub.2CH.sub.2--, --CH.dbd.CH-- or
--CH(CH.sub.3)CH(CH.sub.3)--). In some embodiments L is the
unsubstituted alkylene, and more preferably L is an acyclic
unsubstituted alkylene, and still more preferably the acyclic
unsubstituted alkylene is --CH.sub.2CH.sub.2--,
--CH.sub.2CH(CH.sub.2)--, cis-CH(CH.sub.3)CH(CH.sub.3)--,
trans-CH(CH.sub.3)CH(CH.sub.3)--.
In some embodiments L is the unsubstituted 1,2-cycloalkylene, and
more preferably L is 1,2-cyclopentane-diyl or 1,2-cyclohexane-diyl.
In some embodiments L is the substituted cycloalkylene. In other
embodiments L is substituted or unsubstituted 1,2-arylene or
1,2-heteroarylene (e.g., L is 1,2-phenylene-, 2,3-naphthalene or
2,3-pyridyl). In still other embodiments L is substituted or
unsubstituted two-atom heterohydrocarbylene. In some embodiments L
comprises the 2-atom linker backbone (e.g., L is
--CH.sub.2CH(OCH.sub.3)-- or --CH.sub.2Si(CH.sub.3).sub.2--).
Certain R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b groups are
preferred. In some embodiments one of R.sup.1a, R.sup.2a, R.sup.1b,
and R.sup.2b independently is a (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2,
OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, CN,
CF.sub.3, F.sub.3CO, halogen atom; and each of the others of
R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b is a hydrogen atom. In
some such embodiments it is each of R.sup.2a, R.sup.1b, and
R.sup.2b that is a hydrogen atom. In other such embodiments it is
each of R.sup.1a, R.sup.1b, and R.sup.2b that is a hydrogen
atom.
In some embodiments two of R.sup.1a, R.sup.2a, R.sup.1b, and
R.sup.2b independently are a hydrocarbyl, heterohydrocarbyl, or
halogen atom; and each of the others of R.sup.1a, R.sup.2a,
R.sup.1b, and R.sup.2b is a hydrogen atom. In some such embodiments
it is each of R.sup.1b and R.sup.2b that is a hydrogen atom. In
other such some embodiments it is each of R.sup.2a and R.sup.2b
that is a hydrogen atom. In still other such some embodiments it is
each of R.sup.1a and R.sup.1b that is a hydrogen atom.
In some embodiments three of R.sup.1a, R.sup.2a, R.sup.1b, and
R.sup.2b independently are a hydrocarbyl, heterohydrocarbyl, or
halogen atom; and the other of R.sup.1a, R.sup.2a, R.sup.1b, and
R.sup.2b is a hydrogen atom. In some such embodiments it is
R.sup.1b that is a hydrogen atom. In other such embodiments it is
R.sup.2b that is a hydrogen atom.
In some embodiments each of R.sup.1a, R.sup.2a, R.sup.1b, and
R.sup.2b independently is a (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2,
OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, CN,
CF.sub.3, F.sub.3CO or halogen atom.
In some embodiments one of R.sup.1a and R.sup.1b independently is a
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO, halogen atom, and the
other of R.sup.1a and R.sup.1b independently is a hydrogen atom, a
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or halogen atom. In some
embodiments one of R.sup.1a and R.sup.1b independently is a
hydrocarbyl, heterohydrocarbyl or halogen atom, and the other of
R.sup.1a and R.sup.1b independently is a hydrogen atom,
hydrocarbyl, heterohydrocarbyl, or halogen atom. In some
embodiments each of R.sup.1a and R.sup.1b independently is a
hydrocarbyl or halogen atom. In some embodiments at least one of
R.sup.1a and R.sup.1b is hydrocarbyl. In some embodiments at least
one of R.sup.1a and R.sup.1b is halogen atom.
In some embodiments one of R.sup.2a and R.sup.2b independently is a
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or halogen atom, and the
other of R.sup.2a and R.sup.2b independently is a hydrogen atom,
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or halogen atom. In some
embodiments one of R.sup.2a and R.sup.2b independently is a
hydrocarbyl, heterohydrocarbyl or halogen atom, and the other of
R.sup.2a and R.sup.2b independently is a hydrogen atom,
hydrocarbyl, heterohydrocarbyl, or halogen atom. In some
embodiments each of R.sup.2a and R.sup.2b independently is a
hydrocarbyl or halogen atom. In some embodiments at least one of
R.sup.2a and R.sup.2b is hydrocarbyl. In some embodiments at least
one of R.sup.2a and R.sup.2b is halogen atom.
Certain combinations of R.sup.1a, R.sup.1b, R.sup.2a, and R.sup.2b
are preferred. In some embodiments each of R.sup.1a and R.sup.1b is
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO, halogen atom; and
preferably each of R.sup.2a and R.sup.2b is a hydrogen,
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or halogen atom.
In some embodiments each of R.sup.1a and R.sup.1b is
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
halogen atom; and preferably each of R.sup.2a and R.sup.2b is a
hydrogen, (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl or halogen atom.
In some embodiments at least three of R.sup.1a, R.sup.1b, R.sup.2a,
and R.sup.2b independently is a hydrocarbyl, heterohydrocarbyl, or
halogen atom; and the remaining one of R.sup.1a, R.sup.1b,
R.sup.2a, and R.sup.2b independently is a hydrogen atom,
hydrocarbyl, heterohydrocarbyl, or halogen atom. In some
embodiments at least three and in other embodiments each of
R.sup.1a, R.sup.1b, R.sup.2a, and R.sup.2b independently is a
hydrocarbyl or halogen atom.
In some embodiments R.sup.1a is a hydrogen atom; R.sup.1b is a
hydrocarbyl, heterohydrocarbyl, or halogen atom; R.sup.2a
independently is a hydrocarbyl, heterohydrocarbyl, or halogen atom;
and R.sup.2b independently is a hydrogen atom, hydrocarbyl,
heterohydrocarbyl, or halogen atom. In some embodiments R.sup.1b
independently is hydrocarbyl or halogen atom.
In some embodiments each of R.sup.1a and R.sup.1b is a hydrogen
atom; and at least one, and preferably each of R.sup.2a and
R.sup.2b independently is a hydrocarbyl, heterohydrocarbyl, or
halogen atom. In some embodiments at least one and preferably each
of the R.sup.2a and R.sup.2b independently is hydrocarbyl or
halogen atom. Certain combinations of R.sup.2a, R.sup.2b, R.sup.3a,
and R.sup.3b are preferred. In some embodiments R.sup.2a is a
hydrogen atom; R.sup.2b is a (C.sub.1-C.sub.40)hydrocarbyl,
(C.sub.1-C.sub.40)heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2,
OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, CN,
CF.sub.3, F.sub.3CO or halogen atom; R.sup.3a independently is a
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or halogen atom; and
R.sup.3b independently is a hydrogen atom,
(C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)heterohydrocarbyl,
N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3,
Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or halogen atom. In some
embodiments R.sup.2b independently is hydrocarbyl or halogen
atom.
Certain combinations of R.sup.2a, R.sup.2b, R.sup.3a, and R.sup.3b
are preferred. In some embodiments R.sup.2a is a hydrogen atom;
R.sup.2b is a hydrocarbyl, heterohydrocarbyl, or halogen atom;
R.sup.3a independently is a hydrocarbyl, heterohydrocarbyl, or
halogen atom; and R.sup.3b independently is a hydrogen atom,
hydrocarbyl, heterohydrocarbyl, or halogen atom. In some
embodiments R.sup.2b independently is hydrocarbyl or halogen
atom.
Certain combinations of R.sup.1a, R.sup.1b, R.sup.2a, R.sup.2b,
R.sup.3a, and R.sup.3b are more preferred. In some embodiments
R.sup.2a and R.sup.2b are each hydrogen atom and R.sup.1a,
R.sup.1b, R.sup.3a, and R.sup.3b independently is hydrocarbyl,
heterohydrocarbyl, or halogen atom; and more preferably R.sup.2a
and R.sup.2b are each hydrogen atom and each of R.sup.1a and
R.sup.1b independently is (C.sub.1-C.sub.6)hydrocarbyl,
(C.sub.1-C.sub.5)heterohydrocarbyl, fluorine atom, or chlorine
atom, and each of R.sup.3a, and R.sup.3b independently is
(C.sub.1-C.sub.12)hydrocarbyl, (C.sub.1-C.sub.11)heterohydrocarbyl,
fluorine atom, chlorine atom, or bromine atom. In some embodiments
R.sup.1a and R.sup.1b are each hydrogen atom; each of R.sup.2a and
R.sup.2b independently is (C.sub.1-C.sub.8)hydrocarbyl,
(C.sub.1-C.sub.7)heterohydrocarbyl, fluorine atom, chlorine atom,
or bromine atom; and each of R.sup.3a, and R.sup.3b independently
is (C.sub.1-C.sub.12)hydrocarbyl,
(C.sub.1-C.sub.11)heterohydrocarbyl, fluorine atom, chlorine atom,
or bromine atom.
Preferably each hydrocarbyl, whenever used to define R.sup.1a or
R.sup.1b, independently is an alkyl or cycloalkyl. Preferably the
alkyl is (C.sub.1-C.sub.12)alkyl, more preferably
(C.sub.1-C.sub.8)alkyl, still more preferably
(C.sub.1-C.sub.6)alkyl, and even more preferably
(C.sub.1-C.sub.4)alkyl. Preferably the cycloalkyl is
(C.sub.3-C.sub.6)cycloalkyl, and more preferably
(C.sub.3-C.sub.4)cycloalkyl. Preferably the
(C.sub.3-C.sub.4)cycloalkyl is cyclopropyl. Preferably the
(C.sub.1-C.sub.4)alkyl is methyl, ethyl, 1-propyl, 2-propyl,
1-butyl, 2-butyl, 2-methylpropyl, or 1,1-dimethylethyl, and more
preferably methyl, ethyl, 2-propyl, or 1,1-dimethylethyl. In some
embodiments the (C.sub.1-C.sub.4)alkyl is ethyl, 2-propyl, or
1,1-dimethylethyl. Preferably each halogen atom, whenever used to
define R.sup.1a, R.sup.1b, R.sup.2a, R.sup.2b, R.sup.3a, and
R.sup.3b, independently is a fluorine atom, chlorine atom, bromine
atom or iodine atom.
In some embodiments each of R.sup.1a, R.sup.1b, R.sup.3a, and
R.sup.3b independently is methyl; ethyl; 2-propyl;
1,1-dimethylethyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy;
1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom;
cyano; nitro; dimethylamino; aziridin-1-yl; or cyclopropyl. In some
embodiments at least one, and in some embodiments each of R.sup.2a
and R.sup.2b is a hydrogen atom and each of R.sup.1a, R.sup.1b,
R.sup.3a, and R.sup.3b independently is methyl; ethyl; 1-propyl;
2-propyl; 1-butyl; 1,1-dimethylethyl; cyano; dimethylamino;
methoxy; trifluoromethyl; bromine atom; fluorine atom, or chlorine
atom.
In some embodiments of the metal-ligand complex of formula (I) each
of R.sup.1a and R.sup.1b is a hydrogen atom and at least one, and
in some embodiments each of R.sup.2a, R.sup.2b, R.sup.3a, and
R.sup.3b independently is methyl; ethyl; 2-propyl;
1,1-dimethylethyl; mono-, di-, or trifluoromethyl; methoxy; ethoxy;
1-methylethoxy; mono-, di-, or trifluoromethoxy; halogen atom;
cyano; nitro; dimethylamino; aziridin-1-yl; or cyclopropyl. In some
embodiments at least one, and in some embodiments each of R.sup.1a
and R.sup.1b is a hydrogen atom and each of R.sup.2a, R.sup.2b,
R.sup.3a, and R.sup.3b independently is methyl; ethyl; 1-propyl;
2-propyl; 1-butyl; 1,1-dimethylethyl; cyano; dimethylamino;
methoxy; trifluoromethyl; bromine atom; fluorine atom, or chlorine
atom.
In some embodiments in the metal-ligand complex of formula (I) one
of R.sup.1a and R.sup.1b is methyl; the other of R.sup.1a and
R.sup.1b is as in any one of the preferred embodiments described
herein. More preferably in some of such embodiments each of
R.sup.2a and R.sup.2b is a hydrogen atom and each of R.sup.3a and
R.sup.3b independently is as in any one of the preferred
embodiments described herein.
In some embodiments in the metal-ligand complex of formula (I) at
least one, and more preferably each of R.sup.1a and R.sup.1b
independently is ethyl; 2-propyl; mono-, di-, or trifluoromethyl;
methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy;
halogen atom; cyano; nitro; dimethylamino; aziridin-1-yl; or
cyclopropyl. More preferably in such embodiments at least one, and
more preferably each of R.sup.2a and R.sup.2b, is a hydrogen atom
and each of R.sup.3a and R.sup.3b independently is as in any one of
the preferred embodiments described herein. In some of such
embodiments preferably at least one, and more preferably each of
R.sup.1a and R.sup.1b, is a halogen atom or (C.sub.1-C.sub.6)alkyl,
and still more preferably a (C.sub.1-C.sub.4)alkyl, fluorine or
chlorine atom. In some embodiments at least one, and preferably
each of R.sup.1a and R.sup.1b, is the fluorine atom. In some
embodiments at least one, and preferably each of R.sup.1a and
R.sup.1b, is the chlorine atom. In some embodiments at least one,
and preferably each of R.sup.1a and R.sup.1b, is
(C.sub.1-C.sub.4)alkyl, and more preferably methyl. In general any
combination of R.sup.1a and R.sup.1b, R.sup.2a and R.sup.2b, and
R.sup.3a and R.sup.3b may be made, within the selections provided,
enabled, or exemplified.
In some embodiments of the metal-ligand complex of formula (I) or
the ligand of formula (Q), at least one of R.sup.1a, R.sup.1b,
R.sup.3a, R.sup.3b, R.sup.7c, and R.sup.7d is not methyl. In some
embodiments of the metal-ligand complex of formula (I) at least one
of R.sup.7c, R.sup.7d, R.sup.3a, and R.sup.3b is not methyl.
Certain R.sup.4a and R.sup.4b are preferred. In some embodiments
each of R.sup.4a and R.sup.4b is a hydrogen atom. In some
embodiments at least one and in some embodiments each of R.sup.4a
and R.sup.4b independently is as defined previously for R.sup.1a
and R.sup.1b, respectively. When R.sup.4a or R.sup.4b independently
is as defined previously for R.sup.1a, or R.sup.1b, respectively,
or both, R.sup.4a and R.sup.1a independently may be the same or
different and R.sup.4b and R.sup.1b independently may be the same
or different. In some embodiments at least one, and in some
embodiments each of R.sup.4a and R.sup.4b independently is methyl;
ethyl; 1-propyl; 2-propyl; 1-butyl; 1,1-dimethylethyl; cyano;
dimethylamino; methoxy; trifluoromethyl; bromine atom; fluorine
atom, or chlorine atom.
Certain R.sup.5c and R.sup.5d are preferred. In some embodiments
R.sup.5c and R.sup.5d are the same as each other. In some
embodiments R.sup.5c and R.sup.5d are different from each
other.
In some embodiments at least one, and more preferably each of
R.sup.5c and R.sup.5d independently is (C.sub.6-C.sub.40)aryl.
Preferably the (C.sub.6-C.sub.40)aryl is a (C.sub.6-C.sub.18)aryl
and more preferably (C.sub.6-C.sub.12)aryl. In some embodiments the
(C.sub.6-C.sub.40)aryl is a substituted phenyl and preferably a
2,4-disubstituted phenyl wherein each substituent is R.sup.S,
2,5-disubstituted phenyl wherein each substituent is R.sup.S; or
2,6-disubstituted phenyl wherein each substituent is R.sup.S; and
more preferably wherein each R.sup.S independently is phenyl,
methyl, ethyl, isopropyl, or tertiary-butyl, and still more
preferably 2,6-dimethylphenyl or 2,6-diisopropylphenyl. In some
embodiments the (C.sub.6-C.sub.40)aryl is a 3,5-disubstituted
phenyl wherein each substituent is R.sup.S, and more preferably
wherein each R.sup.S independently is phenyl, methyl, ethyl
isopropyl, or tertiary-butyl, and still more preferably
3,5-di(tertiary-butyl)phenyl or 3,5-diphenylphenyl. In some
embodiments the (C.sub.6-C.sub.40)aryl is a 2,4,6-trisubstituted
phenyl wherein each substituent is R.sup.S, and more preferably
wherein each R.sup.S independently is phenyl, methyl, isopropyl, or
tertiary-butyl; In some embodiments the (C.sub.6-C.sub.40)aryl is a
naphthyl or substituted naphthyl wherein each substituent is
R.sup.S, and more preferably wherein each R.sup.S independently is
phenyl, methyl, ethyl, isopropyl, or tertiary-butyl, and still more
preferably 1-naphthyl, 2-methyl-1-naphthyl, or 2-naphthyl. In some
embodiments the (C.sub.6-C.sub.40)aryl is a
1,2,3,4-tetrahydronaphthyl, and more preferably
1,2,3,4-tetrahydronaphth-5-yl or 1,2,3,4-tetrahydronaphth-6-yl. In
some embodiments the (C.sub.6-C.sub.40)aryl is an anthracenyl, and
more preferably anthracen-9-yl. In some embodiments the
(C.sub.6-C.sub.40)aryl is a 1,2,3,4-tetrahydro-anthracenyl, and
more preferably 1,2,3,4-tetrahydroanthracen-9-yl. In some
embodiments the (C.sub.6-C.sub.40)aryl is a
1,2,3,4,5,6,7,8-octahydroanthracenyl, and more preferably
1,2,3,4,5,6,7,8-octahydroanthracen-9-yl, In some embodiments the
(C.sub.6-C.sub.40)aryl is a phenanthrenyl, and more preferably a
phenanthren-9-yl. In some embodiments the (C.sub.6-C.sub.40)aryl is
a 1,2,3,4,5,6,7,8-octahydrophenanthrenyl, and more preferably
1,2,3,4,5,6,7,8-octahydro-phenanthren-9-yl. As mentioned before,
each of the aforementioned (C.sub.6-C.sub.40)aryl independently is
unsubstituted or substituted by one or more substituents R.sup.S.
In some embodiments the (C.sub.6-C.sub.40)aryl is unsubstituted.
Preferred unsubstituted (C.sub.6-C.sub.40)aryl is unsubstituted
inden-6-yl; 2,3-dihydro-1H-inden-6-yl; naphthalene-2-yl; or
1,2,3,4-tetrahydronaphthalen-6-yl; and more preferably
unsubstituted naphthalen-1-yl; 1,2,3,4-tetrahydronaphthalen-5-yl;
anthracen-9-yl; 1,2,3,4-tetrahydroanthracen-9-yl; or
1,2,3,4,5,6,7,8-octahydroanthracen-9-yl. As mentioned for
(C.sub.6-C.sub.40)aryl hereinabove, each of the aforementioned
(C.sub.6-C.sub.40)aryl independently is unsubstituted or
substituted by one or more substituents R.sup.S. In some
embodiments the (C.sub.6-C.sub.40)aryl is substituted by from 1 to
4 R.sup.S, wherein R.sup.S is as described previously. Preferably
there are 1 or 2 R.sup.S substituents in each substituted
(C.sub.6-C.sub.40), and more preferably 2 R.sup.S substituents in
each substituted phenyl. Preferably each R.sup.S of the substituted
(C.sub.6-C.sub.40)aryl of R.sup.5c and R.sup.5d independently is an
unsubstituted (C.sub.3-C.sub.10)hydrocarbyl, more preferably an
unsubstituted (C.sub.4-C.sub.8)hydrocarbyl, still more preferably
phenyl or an unsubstituted (C.sub.4-C.sub.10)alkyl, and even more
preferably an unsubstituted tertiary (C.sub.4-C.sub.8)alkyl (e.g.,
tertiary-butyl or tertiary-octyl (i.e., 1,1-dimethylhexyl)).
Examples of preferred substituted (C.sub.6-C.sub.40)aryl are a
2,6-disubstituted-phenyl having same substituent R.sup.S (e.g.,
2,6-dimethylphenyl; 2,6-diethylphenyl;
2,6-bis(1-methylethyl)phenyl; and 2,6-diphenyl-phenyl); a
3,5-disubstituted-phenyl having same substituent R.sup.S (e.g.,
3,5-dimethylphenyl; 3,5-bis(trifluoromethyl)phenyl;
3,5-bis(1-methylethyl)phenyl; and 3,5-bis(1,1-dimethylethyl)phenyl;
and 3,5-diphenyl-phenyl); 2,4,6-trisubstituted-phenyl having same
substituent R.sup.S (e.g., 2,4,6-trimethylphenyl; and
2,4,6-tris(1-methylethyl)phenyl);
1-methyl-2,3-dihydro-1H-inden-6-yl;
1,1-dimethyl-2,3-dihydro-1H-inden-6-yl;
1-methyl-1,2,3,4-tetrahydro-naphthalen-5-yl; and
1,1-dimethyl-1,2,3,4-tetrahydronaphthalen-5-yl.
In some embodiments at least one, and more preferably each of
R.sup.5c, and R.sup.5d independently is heteroaryl. Preferably the
heteroaryl has at least one nitrogen atom-containing aromatic ring.
More preferably the heteroaryl is a pyridinyl, indolyl, indolinyl,
quinolinyl, 1,2,3,4-tetrahydroquinolinyl, isoquinolinyl,
1,2,3,4-tetrahydroisoquinolinyl, carbazolyl,
1,2,3,4-tetrahydrocarbazolyl, or
1,2,3,4,5,6,7,8-octahydrocarbazolyl. In some embodiments the
heteroaryl is carbazolyl or a substituted carbazolyl, preferably a
2,7-disubstituted carbazolyl or 3,6-disubstituted carbazolyl, and
more preferably 2,7-disubstituted 9H-carbazol-9-yl or
3,6-disubstituted 9H-carbazol-9-yl, wherein each substituent is
R.sup.S, more preferably wherein each R.sup.S independently is
phenyl, methyl, ethyl, isopropyl, or tertiary-butyl, still more
preferably 3,6-di(tertiary-butyl)-carbazolyl,
3,6-di(tertiary-octyl)-carbazolyl, 3,6-diphenylcarbazolyl, or
3,6-bis(2,4,6-trimethylphenyl)-carbazolyl, and more preferably
3,6-di(tertiary-butyl)-carbazol-9-yl,
3,6-di(tertiary-octyl)-carbazol-9-yl, 3,6-diphenylcarbazol-9-yl, or
3,6-bis(2,4,6-trimethylphenyl)-carbazol-9-yl. Examples of
2,7-disubstituted carbazolyl are the foregoing 3,6-disubstituted
carbazolyl where the 3,6-substituents are moved to 2,7-positions,
respectively. Tertiary-octyl is 1,1-dimethylhexyl. In some
embodiments the heteroaryl is 1,2,3,4-tetrahydrocarbazolyl,
preferably a 1,2,3,4-tetrahydrocarbazol-9-yl. As mentioned before
for heteroaryl, each of the aforementioned heteroaryl independently
is unsubstituted or substituted by one or more substituents
R.sup.S. Preferably each of the indolyl, indolinyl, and tetrahydro-
and octahydro-containing heteroaryl is bonded via its ring nitrogen
atom to the phenyl rings bearing R.sup.5c, or R.sup.5d in formula
(I). In some embodiments the heteroaryl is unsubstituted. Preferred
unsubstituted heteroaryl is unsubstituted quinolin-4-yl,
quinolin-5-yl, or quinolin-8-yl, (the quinolinyl N being at
position 1); 1,2,3,4-tetrahydroquinolin-1-yl (the
tetrahydroquinolinyl N being at position 1); isoquinolin-1-yl,
isoquinolin-4-yl, isoquinolin-5-yl, or isoquinolin-8-yl (the
isoquinolinyl N being at position 2);
1,2,3,4-tetrahydroisoquinolin-2-yl (the tetrahydroisoquinolinyl N
being at position 2); 1H-indol-1-yl (the indolyl N being at
position 1); 1H-indolin-1-yl (the indolinyl N being at position 1);
9H-carbazol-9-yl (the carbazolyl N being at position 9), which may
also be named as a dibenzo-1H-pyrrole-1-yl;
1,2,3,4-tetrahydrocarbazolyl-9-yl (the tetrahydrocarbazolyl N being
at position 9); or 1,2,3,4,5,6,7,8-octahydrocarbazolyl-9-yl (the
octahydrocarbazolyl N being at position 9). In some embodiments the
heteroaryl is substituted by from 1 to 4 R.sup.S. Preferably there
are 1 or 2 R.sup.S substituents in each substituted heteroaryl.
Preferably each R.sup.S of the substituted heteroaryl of R.sup.5c
and R.sup.5d independently is an unsubstituted
(C.sub.3-C.sub.10)hydrocarbyl, more preferably an unsubstituted
(C.sub.4-C.sub.8)hydrocarbyl, still more preferably phenyl or an
unsubstituted (C.sub.4-C.sub.10)alkyl, and even more preferably an
unsubstituted tertiary (C.sub.4-C.sub.8)alkyl (e.g., tertiary-butyl
or tertiary-octyl (i.e., 1,1-dimethylhexyl)). Preferably the
substituted heteroaryl is a 2,7-disubstituted quinolin-4-yl,
2,7-disubstituted quinolin-5-yl, or 3,6-disubstituted
quinolin-8-yl; 3,6-disubstituted 1,2,3,4-tetrahydroquinolin-1-yl;
4-monosubstituted isoquinolin-5-yl; 2-monosubstituted
1,2,3,4-tetrahydroisoquinolin-2-yl; 3-monosubstituted
1H-indol-1-yl; 3-monosubstituted 1H-indolin-1-yl; 2,7-disubstituted
9H-carbazol-9-yl; 3,6-disubstituted 9H-carbazol-9-yl;
3,6-disubstituted 1,2,3,4-tetrahydrocarbazolyl-9-yl; or
3,6-disubstituted 1,2,3,4,5,6,7,8-octahydrocarbazolyl-9-yl.
Examples of preferred substituted heteroaryl are
4,6-bis(1,1-dimethylethyl)pyridine-2-yl; 4,6-diphenylpyridin-2-yl;
3-phenyl-1H-indol-1-yl; 3-(1,1-dimethylethyl)-1H-indol-1-yl;
3,6-diphenyl-9H-carbazol-9-yl;
3,6-bis[2',4',6'-tris(1,1-dimethylphenyl)]-9H-carbazol-9-yl; and
more preferably each of R.sup.5c and R.sup.5d is
3,6-bis(1,1-dimethylethyl)-9H-carbazol-9-yl. The term "tertiary
butyl" means 1,1-dimethylethyl. More preferably R.sup.5c and
R.sup.5d are defined as in any one of the Examples described
later.
In some embodiments of the metal-ligand complex of formula (I) each
Z is O, each of R.sup.2a and R.sup.2b is a hydrogen atom, and each
of R.sup.5c and R.sup.5d independently is the heteroaryl. More
preferred in such embodiments is a metal-ligand complex of any one
of formulas (Ia) to (Ie):
##STR00002## ##STR00003## wherein M, X, R.sup.1a, R.sup.1b,
R.sup.3a, R.sup.3b, R.sup.7c, R.sup.7d, and L are as defined
previously and each R.sup.55 and R.sup.65 is as defined previously.
Preferably each R.sup.55 and R.sup.65 independently is a hydrogen
atom or an unsubstituted (C.sub.1-C.sub.12)alkyl.
In some embodiments the metal-ligand complex of formula (I) each Z
is O, each of R.sup.1a, and R.sup.1b is a hydrogen atom, and each
of R.sup.5c and R.sup.5d independently is the heteroaryl. More
preferred in such embodiments is a metal-ligand complex of any one
of formulas (If) to (Ij):
##STR00004## ##STR00005## wherein M, X, R.sup.2a, R.sup.2b,
R.sup.3a, R.sup.3b, R.sup.7c, R.sup.7d, and L are as defined
previously and each R.sup.55 and R.sup.65 is as defined previously.
Preferably each R.sup.55 and R.sup.65 independently is a hydrogen
atom or an unsubstituted (C.sub.1-C.sub.12)alkyl.
In some embodiments the metal-ligand complex of formula (I) each Z
is O, each of R.sup.2a and R.sup.2b is a hydrogen atom, and each of
R.sup.5c and R.sup.5d independently is the (C.sub.6-C.sub.40)aryl.
More preferred in such embodiments is a metal-ligand complex of any
one of formulas (Ik) to (Io):
##STR00006## ##STR00007## wherein M, X, R.sup.1a, R.sup.1b,
R.sup.3a, R.sup.3b, R.sup.7c, R.sup.7d, and L are as defined
previously and each R.sup.55 and R.sup.65 is as defined previously.
Preferably each R.sup.55 and R.sup.65 independently is a hydrogen
atom or an unsubstituted (C.sub.1-C.sub.12)alkyl.
As mentioned above for the metal-ligand complex of any one of
formulas (Ia) to (Io), the M, X, L, R.sup.1a, R.sup.2a, R.sup.3a,
R.sup.1b, R.sup.2b, R.sup.3b, R.sup.7c, and R.sup.7d, as the case
may be, are as defined for the same of formula (I) (i.e., as M, X,
L, R.sup.1a, R.sup.2a, R.sup.3a, R.sup.1b, R.sup.2b, R.sup.3b,
R.sup.7c, and R.sup.7d of formula (I)). Preferably M is hafnium or
zirconium. Preferably each X is a monodentate ligand. In some
embodiments of the metal-ligand complex of any one of formulas (Ia)
to (Io), n is 2 or 3 and at least two X independently are
monoanionic monodentate ligands and a third X, if present, is a
neutral monodentate ligand. In some embodiments L is
--CH.sub.2CH.sub.2--, --CH(CH.sub.3)CH(CH.sub.3)--,
--CH.sub.2C(CH.sub.3).sub.2--, or --Si(CH.sub.3).sub.2CH.sub.2--.
In some embodiments each of R.sup.1a, R.sup.2a, R.sup.3a, R.sup.1b,
R.sup.2b, R.sup.3b independently is hydrogen atom, methyl; ethyl;
2-propyl; 1,1-dimethylethyl; mono-, di-, or trifluoromethyl;
methoxy; ethoxy; 1-methylethoxy; mono-, di-, or trifluoromethoxy;
halogen atom; cyano; nitro; dimethylamino; aziridin-1-yl; or
cyclopropyl, wherein at least one of R.sup.1a, R.sup.2a, and
R.sup.3a independently is not the hydrogen atom and at least one of
R.sup.1b, R.sup.2b, and R.sup.3b independently is not the hydrogen
atom. In some embodiments each of R.sup.7c and R.sup.7d
independently is (C.sub.4-C.sub.8)alkyl.
The invention process employs catalytic amounts of the invention
catalyst. When more than one catalyst is employed, each catalyst
independently will be in a catalytic amount. The term "catalytic
amount" means less than a stoichiometric quantity based on number
of moles of a product-limiting stoichiometric reactant employed in
the invention process. The catalytic amount is also equal to or
greater than a minimum amount of the metal-ligand complex of
formula (I) that is necessary for at least some product of the
catalyzed reaction to be formed and detected (e.g., by mass
spectrometry). The minimum catalytic amount preferably is 0.0001
mole percent of the number of moles of a product-limiting
stoichiometric reactant. In the invention process the
product-limiting stoichiometric reactant for the invention catalyst
typically will be ethylene. Preferably, the catalytic amount of the
metal-ligand complex of formula (I) used to prepare the invention
catalyst is from 0.001 mol % to 50 mol % of the moles of ethylene
or (C.sub.3-C.sub.40).alpha.-olefin, whichever is lower. More
preferably, the catalytic amount of the metal-ligand complex of
formula (I) is at least 0.01 mol %, still more preferably at least
0.05 mol %, and even more preferably at least 0.1 mol %. Also more
preferably, the catalytic amount of the metal-ligand complex of
formula (I) is 40 mol % or less, and still more preferably 35 mol %
or less.
Preferably the catalyst has a minimum catalyst efficiency or
higher. The catalyst efficiency is calculated by dividing the
number of grams of polyethylene, poly-.alpha.-olefin, or
poly(co-ethylene-.alpha.-olefin), prepared by the number of grams
of metal (M) in ingredient (a) (i.e., M in metal-ligand complex of
formula (I)) employed (i.e., catalyst efficiency=g PE prepared/g M
in metal-ligand complex of formula (I) employed). Preferably when
the catalyst efficiency is determined employing ethylene and
1-octene at a polymerization reaction temperature of 170.degree. C.
and 0.10 micromole (.mu.mol) of the metal-ligand complex of formula
(I), 0.12 .mu.mol of the activating co-catalyst,
bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate
([HNMe(C.sub.18H.sub.37).sub.2][B(C.sub.6F.sub.5).sub.4],
abbreviated as BOMATPB), and 1.0 .mu.mol of another activating
co-catalyst that is a triisobutylaluminum-modified
methylalumoxane-3A (MMAO-3A), hydrogen gas, and a mixed alkanes
solvent, the catalyst efficiency is greater than 740,000, more
preferably greater than 960,000, still more preferably greater than
1,480,000, and even more preferably greater than 1,900,000.
Preferably when the catalyst efficiency is determined employing
ethylene and 1-octene as described later at a polymerization
reaction temperature of 170.degree. C. and 0.08 .mu.mol of the
metal-ligand complex of formula (I), 0.096 .mu.mol of the BOMATPB,
and 0.8 .mu.mol of MMAO-3A, the catalyst efficiency is greater than
1,1,480,000. Preferably when the catalyst efficiency is determined
employing ethylene and 1-octene as described later at a
polymerization reaction temperature of 170.degree. C. and 0.075
.mu.mol of the metal-ligand complex of formula (I), 0.09 .mu.mol of
the BOMATPB, and 0.75 .mu.mol of MMAO-3A, the catalyst efficiency
is greater than 970,000, more preferably greater than 1,060,000,
and still more preferably greater than 1,090,000. Preferably when
the catalyst efficiency is determined employing ethylene and
1-octene as described later at a polymerization reaction
temperature of 170.degree. C. and 0.05 .mu.mol of the metal-ligand
complex of formula (I), 0.06 .mu.mol of the BOMATPB, and 0.5
.mu.mol of MMAO-3A, the catalyst efficiency is greater than
920,000, more preferably greater than 940,000, and still more
preferably greater than 2,900,000. More preferably the catalyst
efficiency is as defined as in any one of the Examples described
later.
In some embodiments, the catalyst, catalyst system or composition,
or both further comprises one or more solvents, diluents, or a
combination thereof. In other embodiments, the such may further
comprise a dispersant, e.g., an elastomer, preferably dissolved in
the diluent. In these embodiments, the catalyst is preferably
homogeneous.
The invention further requires a cocatalyst for activation of the
metal-ligand complex. Where there are two or more such cocatalysts,
they can be activated by the same or different. Many cocatalysts
and activating techniques have been previously taught with respect
to different metal-ligand complexes in the following U.S. Pat. Nos.
5,064,802; 5,153,157; 5,296,433; 5,321,106; 5,350,723; 5,425,872;
5,625,087; 5,721,185; 5,783,512; 5,883,204; 5,919,983; 6,696,379;
and 7,163,907. Preferred cocatalysts (activating co-catalysts) for
use herein include alkyl aluminums; polymeric or oligomeric
alumoxanes (also known as aluminoxanes); neutral Lewis acids; and
non-polymeric, non-coordinating, ion-forming compounds (including
the use of such compounds under oxidizing conditions). A suitable
activating technique is, for example, bulk electrolysis, which is
well known to those skilled in the art. Combinations of one or more
of the foregoing cocatalysts and techniques are also contemplated.
The term "alkyl aluminum" means a monoalkyl aluminum dihydride or
monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl
aluminum halide, or a trialkylaluminum. Preferably the alkyl of the
foregoing alkyl-aluminums is from 1 to 10 carbon atoms.
Triethylaluminum is more preferred. Aluminoxanes and their
preparations are known at, for example, U.S. Pat. No. 6,103,657.
Examples of preferred polymeric or oligomeric alumoxanes are
methylalumoxane, triisobutylaluminum-modified methylalumoxane, and
isobutylalumoxane. Other preferred cocatalysts are
tri((C.sub.6-C.sub.18)aryl)boron compounds and halogenated
(including perhalogenated) derivatives thereof, (e.g.,
tris(pentafluorophenyl)borane, trityl tetrafluoroborate, or, more
preferably bis(octadecyl)methylammonium
tetrakis(pentafluorophenyl)borane
([HNMe(C.sub.18H.sub.37).sub.2]--[B(C.sub.6F.sub.5).sub.4],
abbreviated as BOMATPB)). In some embodiments at least two of the
cocatalysts are used in combination with each other.
The ratio of total number of moles of one or more metal-ligand
complexes of formula (I) to total number of moles of one or more of
the activating co-catalysts is from 1:10,000 to 100:1. Preferably,
the ratio is at least 1:5000, more preferably at least 1:1000; and
10:1 or less, more preferably 1:1 or less. When an alumoxane alone
is used as the activating co-catalyst, preferably the number of
moles of the alumoxane that are employed is at least 100 times the
number of moles of the metal-ligand complex of formula (I). When
tris(pentafluorophenyl)borane alone is used as the activating
co-catalyst, preferably the number of moles of the
tris(pentafluorophenyl)borane that are employed to the total number
of moles of one or more metal-ligand complexes of formula (I) may
vary from 0.5:1 to 10:1, more preferably from 1:1 to 6:1, and still
more preferably from 1:1 to 5:1. The remaining activating
co-catalysts are generally employed in mole quantities that are
approximately equal to the total mole quantities of one or more
metal-ligand complexes of formula (I).
In certain circumstances the comonomer incorporation index may be
determined directly, for example, by the use of NMR spectroscopic
techniques described previously or by IR spectroscopy. If NMR or IR
spectroscopic techniques cannot be used, then any difference in
comonomer incorporation is indirectly determined. For polymers
formed from multiple monomers this indirect determination may be
accomplished by various techniques based on monomer
reactivities.
Olefin polymerizing conditions employed herein independently refer
to reaction conditions such as solvent(s), atmosphere(s),
temperature(s), pressure(s), time(s), and the like that are
preferred for producing, after 15 minutes reaction time, at least a
10 percent (%), more preferably at least 20%, and still more
preferably at least 30% reaction yield of the polyethylene,
poly-.alpha.-olefin, or poly(co-ethylene-.alpha.-olefin) having a
molecular weight less than 2500 Da from the invention process.
Preferably, the process is independently run under an inert
atmosphere (e.g., under an inert gas consisting essentially of, for
example, nitrogen gas, argon gas, helium gas, or a mixture of any
two or more thereof). Other atmospheres are contemplated, however,
and these include sacrificial olefin in the form of a gas and
hydrogen gas (e.g., as a polymerization termination agent). In some
aspects, the process may be run neat, without solvent and with or
without additional ingredients (e.g., catalyst stabilizer such as
triphenylphosphine). In still other aspects, it may be run with a
solvent or mixture of two or more solvents, e.g., an aprotic
solvent. Preferably, the neat process or solvent-based process is
run at a temperature of the neat mixture or solvent-containing
mixture of at least 30.degree. C. to 300.degree. C. A convenient
temperature is from about 40.degree. C. to about 300.degree. C.,
and various embodiments may be run in a range from 60.degree. C.,
or 100.degree. C., or 120.degree. C., to 250.degree. C., or
230.degree. C., or 190.degree. C., or 170.degree. C. Preferably the
process is run under a pressure from about 0.9 atmospheres (atm) to
about 50 atm (i.e., from about 91 kiloPascals (kPa) to about 5050
kPa).
In some embodiments, polymerizable olefins useful in the invention
process are (C.sub.2-C.sub.40)hydrocarbons consisting of carbon and
hydrogen atoms and containing at least 1, and preferably no more
than 3, and more preferably no more than 2, carbon-carbon double
bonds. In some embodiments, from 1 to 4 hydrogen atoms of the
(C.sub.2-C.sub.40)hydrocarbons are replaced, each by a halogen
atom, preferably fluoro or chloro to give halogen atom-substituted
(C.sub.2-C.sub.40)hydrocarbons as the useful polymerizable olefins.
The (C.sub.2-C.sub.40)hydrocarbons (not halogen atom-substituted)
are preferred. Preferred polymerizable olefins (i.e., olefin
monomers) useful for making the polyolefins are ethylene and
polymerizable (C.sub.3-C.sub.40)olefins. The
(C.sub.3-C.sub.40)olefins include an .alpha.-olefin, a cyclic
olefin, styrene, and a cyclic or acyclic diene. In some embodiments
at least one of the other polymerizable olefin is the
.alpha.-olefin, and more preferably a
(C.sub.3-C.sub.40).alpha.-olefin. In some embodiments the
(C.sub.3-C.sub.40) .alpha.-olefin is a
(C.sub.4-C.sub.40).alpha.-olefin, more preferably a
(C.sub.6-C.sub.40).alpha.-olefin, still more preferably a
(C.sub.7-C.sub.40).alpha.-olefin, and even more preferably a
(C.sub.8-C.sub.40).alpha.-olefin. Preferably, the .alpha.-olefin
comprises the (C.sub.3-C.sub.40).alpha.-olefin, more preferably a
branched chain (C.sub.3-C.sub.40).alpha.-olefin, still more
preferably a linear-chain (C.sub.3-C.sub.40).alpha.-olefin, even
more preferably a linear chain (C.sub.3-C.sub.40).alpha.-olefin of
formula (A): CH.sub.2.dbd.CH.sub.2--(CH.sub.2).sub.zCH.sub.3 (A),
wherein z is an integer of from 0 to 40, and yet even more
preferably a linear-chain (C.sub.3-C.sub.40).alpha.-olefin that is
1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,
1-octadecene, or a linear-chain (C.sub.20-C.sub.24).alpha.-olefin.
Preferably the cyclic olefin is a (C.sub.3-C.sub.40)cyclic olefin.
Preferably, the cyclic or acyclic diene is a
(C.sub.4-C.sub.40)diene, preferably an acyclic diene, more
preferably an acyclic conjugated (C.sub.4-C.sub.40)diene, more
preferably an acyclic 1,3-conjugated (C.sub.4-C.sub.40)diene, and
still more preferably 1,3-butadiene.
Polyolefins that can be made by an invention process include, for
example, polyethylene and interpolymers that comprise residuals of
ethylene and one or more polymerizable (C.sub.3-C.sub.40)olefins.
Preferred interpolymers are those prepared by co-polymerizing a
mixture of two or more polymerizable olefins such as, for example,
ethylene/propylene, ethylene/1-butene, ethylene/1-pentene,
ethylene/1-hexene, ethylene/4-methyl-1-pentene, ethylene/1-octene,
ethylene/styrene, ethylene/propylene/-butadiene and other EPDM
terpolymers. Preferably, the polyolefin is an ethylene homopolymer
(e.g., a high density polyethylene), an ethylene/.alpha.-olefin
interpolymer (i.e., poly(co-ethylene .alpha.-olefin), such as, for
example, a poly(ethylene 1-octene)), or an
ethylene/.alpha.-olefin/diene interpolymer (i.e., a poly(ethylene
.alpha.-olefin diene)terpolymer such as, for example, a
poly(ethylene 1-octene 1,3-butadiene).
Preferably, the mole ratio of (moles of
(C.sub.3-C.sub.40).alpha.-olefin)/(moles of ethylene) is 0.1 or
higher, more preferably 0.30 or higher, still more preferably 0.50
or higher, and even more preferably 0.75 or higher (e.g., 1.0 or
higher).
In another embodiment, the present invention is a polyolefin,
preferably the polyethylene (e.g., in an isolated form or as part
of an intermediate mixture with the .alpha.-olefin) prepared by the
invention process.
The inventive process may be run in one reactor or in multiple
reactors. For example, single reactor, multiple catalyst processes
are useful in the present invention. In one embodiment, two or more
catalysts are introduced into a single reactor under the olefin
polymerization conditions, wherein at least the first one of the
catalysts is a catalyst of the group specified herein and each
catalyst inherently produces a mixture or blend of different
polyolefin copolymers. The terms "mixture" and "blend" as applied
to the polyolefin copolymers are synonymous. Use of different
catalysts within the invention may result in similar or different
comonomer incorporation, but products within the invention will
fall into a weight average molecular weight range of less than 2500
Da, preferably less than 1500 Da. Variation of the ratio of two or
more catalysts within a single reactor will vary the product ratio,
and knowledge of such is within that of those skilled in the art.
See also, U.S. Pat. No. 6,924,342. The invention catalysts are
compatible with other olefin polymerization catalysts, including
Ziegler/Natta catalysts. Due to this compatibility, an additional
catalyst included in one reaction may comprise a metallocene or
other .pi.-bonded ligand group containing metal-ligand complex
(including constrained geometry metal-ligand complexes), or a
polyvalent heteroatom ligand group containing metal-ligand complex,
especially polyvalent pyridylamine or imidizolylamine based
complexes and tetradentate oxygen-ligated biphenylphenol based
Group 4 metal-ligand complexes. Preferably, the invention catalyst
is prepared from, and the invention process employs, three or
fewer, more preferably two, and still more preferably one
metal-ligand complex of formula (I) per reactor. Further discussion
of such may be found in co-pending U.S. Patent Publication No.
2011/0282018, filed May 11, 2011.
In some embodiments a preferred invention process can achieve a
minimum molecular weight distribution or polydispersity index (PDI)
of the polyolefin product produced thereby. In some embodiments the
PDI is greater than 2.4, in other embodiments the PDI is greater
than 4.0, in other embodiments the PDI is greater than 6.0, and in
still other embodiments the PDI is greater than 8.0. In some
embodiments the PDI is less than 11.
In some embodiments a preferred invention process can achieve a
productivity ratio of weight of polyolefin produced per weight of
ethylene employed, as determined employing ethylene and 1-octene as
described later at a polymerization reaction temperature of
170.degree. C., wherein the productivity ratio of the polyolefin
produced to ethylene employed is greater than 1.00, preferably
greater than 1.10, more preferably greater than 1.40, and still
more preferably greater than 2.50.
EXAMPLES
General Analysis Procedures
Gel permeation chromatography (GPC): Determine weight average
molecular weight (M.sub.w) and polydispersity index: Determine
M.sub.w and ratio of M.sub.w/M.sub.n (polydispersity index or PDI)
using a Polymer Labs.TM. 210 high temperature gel permeation
chromatograph. Prepare samples using 13 mg of polyethylene polymer
that is diluted with 16 mL of 1,2,4-trichlorobenzene (stabilized
with butylated hydroxy toluene (BHT)), heat and shake at
160.degree. C. for 2 hours.
Determining melting and crystallization temperatures and heat of
fusion by Differential Scanning Calorimetry (DSC; DSC 2910, TA
Instruments, Inc.)); First heat samples from room temperature to
180.degree. C. at a heating rate of 10.degree. C. per minute. After
being held at this temperature for 2 to 4 minutes, cool the samples
to -40.degree. C. at a cooling rate of 10.degree. C. per minute;
hold the sample at the cold temperature for 2 to 4 minutes, and
then heat the sample to 160.degree. C.
Abbreviations (meanings): r.t. (room temperature); g (gram(s)); mL
(milliliter(s)); .degree. C. (degrees Celsius); mmol
(millimole(s)); MHz (MegaHertz); Hz (Hertz).
##STR00008##
Starting Compound
Synthesis Procedures for Metal-Ligand Complexes
Step 1: Preparation of 4-chloro-2-iodo-6-methylphenol
To a stirred solution of 5.08 g (35.63 mmol) of
4-chloro-2-methylphenol, 6.42 g (42.83 mmol) of NaI, and 1.74 g
(43.50 mmol) of NaOH in 70 mL of methanol at 0-10.degree. C. is
added 71 mL (47.69 mmol) of 5% aqueous NaOCl solution (commercial
bleach) dropwise over 1.5 hours. After addition of NaOCl solution
is complete the reaction mixture is stirred for an additional hour
at 0-10.degree. C., then 25 mL of 10 wt. % aqueous sodium
thiosulfate is added. The mixture is acidified using 5% HCl, then
extracted with methylene chloride (i.e., dichloromethane, DCM). The
combined organic phases are washed with an equal volume each of 10
wt. % aqueous sodium thiosulfate, then water, then brine, then
dried over anhydrous magnesium sulfate, then filtered through a pad
of silica gel, and then concentrated to give crude compound. This
crude is recrystallized from hexanes to afford 9.37 g (98%) product
as white needles. .sup.1H NMR showed product is
4-chloro-2-iodo-6-methylphenol.
##STR00009##
Step 2: Preparation of
1,2-bis(4-chloro-2-iodo-6-methylphenoxy)ethane
To a round bottom flask under N.sub.2 atmosphere is added 6.00 g
(22.35 mmol) of 4-chloro-2-iodo-6-methylphenol, 6.18 g (44.72 mmol)
of K.sub.2CO.sub.3, 45 mL of DMF, and 4.14 g (11.18 mmol) of
ethylene glycol ditosylate. The mixture is stirred and refluxed for
18 hours, cooled and concentrated. The residue is treated with
50/50 DCM and water until all solids are dissolved and then
transferred the mixture to a separation funnel where the compound
is extracted into DCM. The organic solution is washed with 2N NaOH,
water then brine, dried over anhydrous magnesium sulfate, filtered
through a pad of silica gel and concentrated to give 4.56 g (72.5%)
of pure product as white solid. .sup.1H NMR shows product is
1,2-bis(4-chloro-2-iodo-6-methylphenoxy)ethane.
##STR00010##
Step 3: Preparation of
2',2'''-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-y-
l)-5'-chloro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol-
)
To a stirred solution of 5.0 g (8.82 mmol) of
3,6-di-tert-butyl-9-(2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phe-
nyl)-9H-carbazole in 75 mL of tetrahydro-furan (THF) at 0.degree.
C. under nitrogen atmosphere 8.1 mL (20.25 mmol) of n-butyllithium
(2.5 M solution in hexanes) is added over a period of 10 minutes.
The solution is stirred at 0.degree. C. for three more hours.
Tri-isopropyl borate (4.8 mL, 20.8 mmol) is added to this and
continued stirring at 0.degree. C. for 1 hour. The mixture is
slowly warmed to room temperature and stirred for 3 more hours at
room temperature. The mixture is concentrated to dryness by rotary
evaporation and 100 mL of ice cold water is added. The mixture is
acidified using 2N HCl and extracted with dichloromethane (DCM).
The DCM solution is washed with water and brine. The solvent is
removed by rotary evaporation and the residue is dissolved in 90 mL
of dimethoxyethane. This solution is then treated with a solution
of 1.06 g (26.5 mmol) of NaOH in 25 mL of water, 25 mL of THF and
2.35 g (4.17 mmol) of
1,2-bis(4-chloro-2-iodo-6-methylphenoxy)ethane. The system is
purged with N and 0.30 g (0.26 mmol) of Pd(PPh.sub.3).sub.4 is
added. The mixture is then heated to 85.degree. C. for 36 hours
under N atmosphere. The mixture is cooled and the volatiles removed
by rotary evaporation. The residue is treated with 100 mL of water
and extracted with DCM. The DCM solution is washed with water and
brine, and dried over anhydrous magnesium sulfate. After removal of
the solvent, the reaction products are dissolved in 150 mL of
THF/MeOH (1:1) and stirred for 5 hours at 50.degree. C. after the
addition of 100 mg of p-toluenesulfonic acid. The solvent is
removed and the product is partially purified by flash
chromatography eluting with 5% ethyl acetate in hexanes. This
product is further purified by crystallization from THF/MeOH
(dissolved in minimum amount of THF and diluted with MeOH until it
became cloudy. It is then heated to obtain a clear solution and
allowed to crystallize in refrigerator). The solid formed is
collected and dried under reduced pressure to afford 3.5 g (62.5%)
of the pure ligand as white solid. .sup.1H NMR shows the product is
2',2'''-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol--
9-yl)-5'-chloro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-
-ol).
##STR00011##
Step 4: Preparation of
(2',2''-(ethane-1,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-ca-
rbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethy-
l-zirconium (Metal-Ligand Complex 1)
To a suspension of 0.75 g (0.59 mmol) of
2',2'''-(ethane-1,2-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-y-
l)-5'-chloro-3'-methyl-5-(2,4,4-tri-methylpentan-2-yl)-[1,1'-biphenyl]-2-o-
l) and 0.137 g (0.59 g) of HfCl.sub.4 in 50 mL of toluene is added
0.84 mL of 3M diethyl ether solution of MeMgBr. After stirring for
1 hr solvent is removed under reduced pressure. To the residue is
added 20 mL of toluene followed by 30 mL of hexane. Suspension is
filtered giving colorless solution. Solvent is removed under
reduced pressure leaving white solid. The residue is suspended in
15 mL of hexane and suspension is stirred for 30 min. The solid is
collected on the frit, washed with 3 mL of hexane and dried under
reduced pressure to give 0.545 g of product as white solid. .sup.1H
NMR shows the product is
(2',2''-(ethane-1,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-ca-
rbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethy-
l-zirconium (Metal-Ligand Complex 1).
##STR00012##
Alternative Step 4: Preparation of
2',2''-(ethane-1,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-car-
bazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-
-hafnium (Metal-Ligand Complex 2)
To a suspension of 1.94 g (1.52 mmol) of ligand and 0.488 g (1.52
mmol) HfCl.sub.4 in 50 mL of toluene is added 2.18 mL of 3M diethyl
ether solution of MeMgBr. After stirring for 1 hr solvent is
removed under reduced pressure. To the residue is added 30 mL of
toluene followed by 30 mL of hexane. Suspension is filtered giving
colorless solution. Solvent is removed under reduced pressure
leaving white solid. The residue is suspended in 12 mL of hexane
and suspension is stirred for 30 min. The solid is collected on the
frit, washed with 3 mL of hexane and dried under reduced pressure
to give 1.81 g of product as white solid. Yield is 80.3%. .sup.1H
NMR spectra of this product are consistent with the desired
structure.
A comparative complex is also prepared and designated as
(Metal-Ligand Complex 3--comparative), as shown hereinbelow.
##STR00013## (Metal-Ligand Complex 3--comparative)
Examples 1-2 and Comparative Example A
Ethylene is polymerized independently using the Metal-Ligand
Complexes (1) and (2), corresponding to Examples 1 and 2, and the
comparative Metal-Ligand Complex (3), corresponding to Comparative
Example A, under the following conditions: 2 L batch reactor,
140.degree. C., 783 g of isoparE, a saturated isoparaffinic
hydrocarbon fluid available from ExxonMobil. Conditions include
ethylene pressure of 460 psi; run time of 10 min. Results include
catalyst efficiency (gPE/gM), calculated by dividing weight in
grams of PE product by weight in grams of metal M in metal-ligand
complex used. M.sub.w (g/mol) is weight average molecular weight in
grams per mole determined by GPC; M.sub.w/M.sub.n=polydispersity
index (PDI)=M.sub.w divided by number average molecular weight
(M.sub.n) (g/mol). Results are shown in Table 1.
TABLE-US-00001 TABLE 1 Polymerization of Ethylene Metal-Ligand
Complex Efficiency/ Name moles metal (g) g Metal Mw Mw/Mn 1 0.03 Zr
8.3 3032828 338 1.19 2 0.04 Hf 13.2 1848843 599 1.47 Comp. Ex. A
0.05 Hf 4.7 526640 2,703 2.06
As shown by the above description, including the Examples, the
invention catalysts prepared from the invention metal-ligand
complexes polymerize ethylene, .alpha.-olefin or ethylene with
.alpha.-olefin to yield the low molecular weight polyethylene,
poly-.alpha.-olefin or poly(co-ethylene-.alpha.-olefin) having a
backbone weight average molecular weight of less than 2500 Da. The
invention process is also useful for preparing the aforementioned
polymer blends with good catalyst efficiency.
* * * * *